Process and apparatus for preparing lead oxides



July 15, 1930. HAYNES 1,770,777

PROCESS AND APPARATUS FOR PREPARING LEAD OXIDES Filed Dec. 23 1925 2 Sheets-Sheet l 7n7perafare In deyree f gwucn fob:

July 15, 1930. P. E; HAYNES 7 PROCESS AND APPARATUS FOR PREPARING LEAD OXIDES I Filed Dec. 23, 192 5 2 Sheets-Sheet 2 Patented July 1930 V UNITED STATES PATENT orrlcs PIERRE E. HAYNES, OF EAST AURORA, NEW YORK, ASSIGNOR TO THE LINDE AIR PRODUCTS'COMPANY,-A CORPORATION OF OHIO PROCESS AND APPARATUS FOR PREPARING LEAD OXIDES Application filed Ilecember 23, 1925 Serial'No. 77,334.

This invention relates to a process and apparatus for the production of oxides of lead,

, and it comprises a process wherein lead is converted into oxides by initially treating molten lead in anoxidizing atmosphere containing oxygen in substantially atmospheric proportion and, as the oxidation proceeds, bringing the partially oxidized mixture into contact with a gas substantially richer, in

0 oxygen. More particularly, the invention in 1ts' preferred form comprises a continuous process forthe manufacture of red lead 1n which the molten lead is passed through an oxidizing zone in countercurrent relation to a stream of an oxidizing gas, the oxygen con-.

tent of which yaries progresslvely from that of air at'the point Where oxidation is commen'ced to that of commercial oxygen at the exit from said zone. The partially oxidized product may be withdrawn at any convenient lead oxides is disclosed in U. S. patent to Huffard and Haynes, 1,491,237, April 22, 1924. In the process there disclosed the speed of as the lead-oxygen reaction is greatly increased by the use of oxygen instead of air and by raising the reaction'temperature by external heating means.

In order to show the technical advantage 40 of the use of oxygen, Fig. 1, containing curves of vapor tensions of lead. and the dissociation pressures of red lead, has been included.

- It is obvious from these curves that lead will become more active in the presence of oxygen as the temperature is increased because of the rapid increase of vapor'tension. It is equally obvious that the increase in temper:

ature increases the tendency of red lead to decompose into monoxide andoxygen. Using an as the oxidlzmg agent it becomes 'is given up by dissociation-as rapidly as it exceedingly difficult and finally impossible to oxidize lead to red lead with air as the temperature is progressively increased because a point is finally reached where oxygen is absorbed. Thus, it "is found that the dissociation pressure of red lead is 21% of one atmosphere at -1012 F. andthis is, therefore, the highest temperature at-which red lead will form using air as the oxidizing agent. As a matter of fact, the removal of oxygen from the air by the lead makes it necessary touse a lower.t emperatur'e and hence the speed of the reaction is reduced;

' On the other hand, when oxygen is used, its advantages are compounded by the fact that in addition to the normal increase in the rate of the reaction due' to the increase in oxygen content of the oxidizing atmosphere, it is possible to employ higher temperatures where the speed of oxidation is greater. Higher temperatures also increase the vapor tension of lead and, therefore, its avidity for oxygen.

Therefore, it will be apparent that the need for higher oxygen content becomes greater as the red lead content is increased. Accordingly I have found that, when oxygen is used in countercurrent relationto lead monoxide and lead or a mixture of the tetroxide, mon oxide and fused metallic lead, the speed of the reaction is much accelerated. Also it has been found possible to use air for the first and major portion of the reaction and then bring the product of this initial treatment into contact with .a gas containing oxygen in proportion substantially greater than atmospheric. This gas is preferably commercial oxygen containing about 98% or more 0 although most of the advantages ofthe invention may be secured by using an oxidizing gas containing a; smaller'proportion of oxygen, if materially in excess 'of thatin air.

. Since the dissociation and melting temperatures of the monoxide are relatively high it will be possible cooperate the initial oxidation at a temperature above the remainder of the reaction and thus take advantage of the increased vapor tension of lead. -As the.

reaction producing the. monoxide progresses it will be possible to reduce the temperature and allow the coloring reaction, in which the monoxide is converted to tetroxide, to start. It is also within the scope of the invention, however, to conduct the oxidation of the monoxide to the tetroxide at temperatures similar to those used in the initial oxidation stage, since with the use of oxygen or an oxygen-enriched atmosphere the temperature at which dissociation of the tetroxide takes place in raised. The range of 930 to 1200 F. is preferred for carrying out the initialoxidation although higher or lower temperatures may be used with good results. The coloring reaction may be carried out at a temperature within the range abovementioned or at a lower temperature as desired.

Another marked advantage of the continuous process which I have devised lies in the conservation of the heat liberated in the ex othermic reaction between the lead and oxygen. Thus the heat from the most energetic phase of the reaction is available for the maintenance of the necessary temperature for the slower phase, and therefore it will be practicable to operate the continuous process with just enough fuel to make up the actual heat requirements including thermal losses.

It has also been found advantageous to withdraw the oxide at some intermediate point and grind it to the fineness ultimately desired. While the point chosen for grinding is purely arbitrary, it is preferred to select the point at which the reaction is slow ing up because unoxidized material is rapidly becoming coated with oxide. Grinding at this point very materially speeds up the oxidation. The heat content of the oxide'withdrawn may also. be utilized for pre-heating the air used for oxidation.

.For a detailed description of the process and apparatus used in carrying out my invention attention is directed tothe accompanying drawing in which Fig. 1 illustrates the curves of vapor tensions and dissociation pressures of lead and red lead, respectively. Fig. 2 is a longitudinal view of the preferred apparatus partly in vertical section and partly in elevation, Fig. 3 is a longitudinal vertical section through a portion of the oxidizing kiln, whileFig. 4 represents a section of %1c oxidizing kiln taken on the line 44 of i 2. lllolten lead supplied from the lead meltwaste combustion ases led from the furnace chamber 2 bysuita le connections not shown. The molten lead-is conducted by an insulated pipe 3 to section a of a rotating externally heated kiln 4. The rotating kiln 4 consists of any suitable number of cast iron flanged sections secured end to end in any suitable way and mounted on ,rollers 5. The kiln-is ing pot 1, WhlCh is preferably heated byrotated by means of gearin 6 and the motor 7. Any desired number 0 sections may be employed, but according to my preferred embodiment eight are used and-are referred to hereafter as a, b, 0, d,e, f, g and it. Between each two sections is a cast iron plate or bafile with a large opening 8 at the center and, with the exception of thebaflle between sections (:3 and e, a plurality of smaller openings 9 positioned equidistantly about the central opening. A bucket 10 is placed opposite each of the smaller openings. These buckets are adapted, as the kiln rotates, to pick up a mixture of oxides and possibly some molten lead. As the bucket rises the molten lead trickles to the bottom of the bucket where it is trapped and escapes through a small opening 11. The oxide'partially or completely freed from metal passes by gravity to the next section.

Gaseous communication is maintained between the various sections by means of the central opening Sin each of the bafile plates Air, 'pre-heated by any suitable means not shown, is forced by the fan 12 through the pipe 13 and passes into the sections a, b and a of the kiln 4 where, coming into contact with the molten lead or with lead monoxide, oxidation takes place according to the reactions:

. 2 Pb+o.=2 Pro 6 PbO+O2=2 P1080.

Substantially pure oxygen is introduced into section 72. by means of pipe 14 leading from any suitable source not shown. As pretakes place with a partial coloring of the lead oxides and in section (Z the mixture of oxides is picked up by buckets 15 attached to thewalls of the kiln and dropped into the hoper 16 of the conveyor 17 which transports it to a point 17 and drops it into a hopper 18 feeding the pulverizer or mill 19. The ground material from the pulverizer or mill 19 is lifted by means of a suitable fan 20 positioned in the conduit 21 to a bag (not shown) and hopper. 22, from which it is fed to conveyor 23 which transports it to section e of the kiln 4. By the method above described the oxidation is continued and the mixture of oxides is passed progressively through-sections 6, f, gand k in contact with progres- The oxygen for the process is led from any suitable source by pipe 27 to the point .27. Valves 28 and-28 provide'for a division of sively richer oxygen; In section ]z.-the prodthe gas flow, the major. portion passing througlr valve 28 and pipe 14 to section 72.

of the drum, whilea smaller portion of theoxygen'passes through valve 28 and pipe 29 to conveyor where it passes in countercurrent relationto red lead and serves to complete the oxidation under 'optimu conditions or mixing and stirring produc' d by the conveyor. This last step is decidedly advan-" tageous since relatively small quantities of oxide are in intimate contact with large quantities of the purest oxygen throughout the complete travel fromsection h. to point26.

The whole kiln is maintained at atmospheric pressure byan annular opening 30 which communicates with the air. To pre-' vent the blowing of oxide dust 1nto the open air a suction fan 311s used to maintain a slight minus pressure in the pipe 32 which extendsthrough the vent cap 33 to a point adjacent the entrance to section a; Thus the. quantity of gas withdrawn through the plpe substantially equals that of the air introduced by the fan 12. The withdrawn gas, together with any oxide particles carried along therewith, is led to a bag33' where the oxide is collected. This oxide may be re turned to the furnace for further treatment.

As will be seen theprocess is entirely automatic and continuous, the elements of control being the quantities of. molt en lead and oxygen. 'Asthe systemis-maintained at at- Y mospheric pressure'no leakage of oxygen will gas containing oxygen materially in excess take place. a The kiln is heated by means of burners 34 which are individually regulable to permit.

of the maintenance of any desired temperature in the different'sections of the kiln.

It is to be understood that the rotation of the kiln will bring about considerable agitation of the lead and oxidesand thus facilitate oxidation. However, agitation of the material may be increased by providing agif tating plates on the walls of the kiln as is. well understood in the art.

Various modifications of the means and procedure by which the advantageous effects of the invention are'obtained, fall within the scope of the appended claims.

I claim:

1. Process of. oxidizing lead, comprising passing molten lead through an oxidizing zone and passing incountercurrentrelation thereto a stream of gas containing oxygen substantially in atmospheric proportion and,

as the oxidation proceeds, leading the mixture of oxides formed into contact. with a .7 of atmospheric proportion.

2. continuous process of oxidizing lead, comprising passing into contact with molten lead a gas contalning oxygen in substantially atmospheric proportion to at least partially oxidize the lead to lead monoxide, and then passmg into contact therewith a gas con taming oxygen materially in excess of atmospheric proportion until the desired oxidation is effected. p I

' 3. A continuous process of producing red lead, comprising partially oxidizing molten lead by passing pre-heated air into contact therewith, commlnuting the resulting product, and then passing commercial oxygen into contact therewith to complete the oxidation. '1 J 4. A continuous'process of oxidizing lead comprising passing molten lead through an oxidizing zone in countercurrent relation'to a stream of gas which at the lead entrance to the oxidizing zone. contains oxygen in substantially atmospheric proportion but, is

progressively richer in oxygen towards the exit from said zone; removing the product and grinding itintroducing the product ll'1-' to a second oxidi-zingzone and subjecting it to a gas containing oxygen materially in excess of atmospheric proportion; and finally intimately mixing and stirring the resulting oxide with relatively large quantities of substantially pure oxygen.

5. Process of oxidizing-lead, comprising initially treating molten lead with air to at least partially oxidize it to monoxide, and then treating the product of the initial treatment with a gas containing oxygen materially in excess of atmospheric proportion until 6. Process of producing 'red lead, comprising treating molten lead with air at a rela-.

tively high temperature to at least partially oxidize it to lead monoxide, and then subjecting the partially oxidized product to further oxidation by passing into contact thereexcess of atmospheric proportion, the further oxidation being carried on at graduated lower temperatures.

the major portion is converted intored lead.

with a gas containing oxygen materially in 7. Processof producing red lead, comprising-initially oxidizing the lead at a relatively high temperature, reducing the temperature as the oxidation progresses, and carrylng on the further-oxidation at graduated lower temperatures.

8'. Process of preparing lead oxides, com-- I prising treating molten lead in an oxidizing zone to partially oxidize the same, separating prising charging moltenlead into a rotary kiln containing a plurality of communicating chambers, leading an oxidizing gas through the furnace in a direction opposite to that of g the movement of the lead, and rotating the furnace to agitate the lead and to advance the oxides progressively through the respective chambers while retaining any residual lead in the initial oxidizing zone. I

11. Apparatus for oxidizing lead, comprising a rotary kiln divided into a plurality of treating chambers, means for lntroducing molten lead into the first chamber, means for introducing an oxidizing gas into the kiln in countercurrent relation to the movement of lead through the kiln, and means adapted as the kiln rotates to separate oxides from the molten lead and to advance them through successive chambers, While retaining the molten lead in the first chamber.

12. Apparatus for oxidizing lead, comprisintroduce' molten lead into the first section, means adapted to advance the oxides formed through successive sections While retaining the molten lead in the first section, and means adapted toconvey material from an intermediate section to a point outside the kiln and to re-introduce it into a succeeding section;

In testimony whereof, I afiix m signature.

PIERRE E. AYNES.

mg a rotary kiln made up of a plurality of communicating sections, means adapted to 

